Oxidative brown hair dye

ABSTRACT

This invention is a composition useful for dyeing keratinous fiber brown without using o-, m- or p-phenylenediamine, 2,4-diaminoanisol or nitro compounds. The composition consists essentially of 1,5-dihydroxynaphthalene, m-aminophenol, p-aminodiphenylamine or a suitable acid addition salt thereof, a suitable modifier, a suitable coupler and a suitable base. This composition in combination with an oxidizing agent dyes hair brown.

BACKGROUND OF THE INVENTION

This invention relates to a dye composition for dyeing keratinous fiberbrown. More specifically, the composition is essentially free of o-, m-or p-phenylenediamine, 2,7-diaminoanisole and nitro compounds. Even morespecifically the invention relates to a composition consisting of1,5-dihydroxynaphthalene, m-aminophenol, p-aminodiphenylamine or asuitable acid addition salt thereof, a suitable modifier, a suitablecoupler and a sufficient amount of a suitable base. When thiscomposition is mixed with a effective amount of oxidizing agent andapplied to keratinous fiber, particularly human hair, the fiber is dyedbrown.

PRIOR ART

It is generally known that commercial oxidative hair dyes require thepresence of o-, m- or p-phenylenediamine or 2,4-diaminoanisole and thedirect dyes require the presence of nitro compounds. However, in recentyears it has been found that these compounds may exhibit a mutagenicreaction in the Ames test either in the oxidized or unoxidized state.See Ames, et al., "Hair Dyes are Mutagenic: Identification of a Varietyof Mutagenic Ingredients" PROC. NAT. ACAD. SCI. U.S.A., 72, No. 6, pp.2423-2427, June, 1975.

While the individual compounds of this invention have been known formany years, these compounds have been used in association with o-,m andp-phenylenediamine, 2,4-diaminoamisole but have never been employed bythemselves because it was thought that the o-, m- or p-phenylenediaminesor 2,4-diaminoanisole were necessary to form the desired shades ofbrown. For discussion of the role of o-, m- or p-phenylenediamine and2,4-diaminoamisole as dye-forming intermediates in oxidation dyes seeThe Chemistry and Manufacture of Cosmetics, Vol. IV, 2nd Edition, editedby Maison G. de Navarre, pages 841-920.

It has now been discovered that a specific unique combination ofpreviously known compounds has been found to give excellent dyes fordyeing keratinous fibers brown without using any o-, m- orp-phenylenediamine, 2,4-diaminoamisole or nitro compounds.

SUMMARY OF THE INVENTION

One aspect of this invention is a composition for dyeing keratinousfiber brown. The composition is essentially free of o-, m- orp-phenylenediamine, 2,4-diaminoanisole and nitro compounds. Thecomposition consists essentially of

ABOUT 0.1 TO 4.0 PARTS BY WEIGHT 1,5-DIHYDROXYNAPHTHALENE,

ABOUT 0.2 TO 2.5 PARTS BY WEIGHT M-AMINOPHENOL,

ABOUT 0.01 TO 1.5 PARTS BY WEIGHT P-AMINODIPHENYLAMINE OR A SUITABLEACID ADDITION SALT THEREOF,

ABOUT 0.5 TO 15.0 PARTS BY WEIGHT OF A SUITABLE MODIFIER,

ABOUT 0.5 TO 7.5 PARTS BY WEIGHT OF A SUITABLE COUPLER, AND

A SUFFICIENT AMOUNT OF A SUITABLE BASE TO MAKE UP A TOTAL OF 100 PARTSBY WEIGHT OF SUCH COMPOSITION.

Another aspect of the invention is a combination of the abovecomposition with a suitable oxidizing agent. This combination may be anactual mixture of the two or may be a combination of the composition andthe oxidizing agent in two separate containers together in a snglepackage.

Still another aspect of the invention is a process for dyeing keratinousfibers, particularly human hair, brown which comprises contacting thefibers with an effective amount of a mixture of the composition and anoxidizing agent for a time sufficient to effect dyeing of the fibers.

FURTHER DESCRIPTION AND PREFERRED EMBODIMENTS

The following table gives the operable ranges in parts by weight (pbw)for each of the components of the novel composition of the invention aswell as the optimum ranges for each of the components.

    ______________________________________                                                   Operable (pbw)                                                                            Optimum (pbw)                                          ______________________________________                                        1,5-dihydroxy-                                                                             0.1-4.0       .25-2.5                                            naphthalene                                                                   m-aminodiphenol                                                                            0.1-2.5       0.2-2.0                                            p-aminophenyl-                                                                             0.01-1.5      0.5-1.0                                            amine (salt)                                                                  modifier     1.0-15.0      1.2-11.0                                           coupler      0.5-7.5       0.6-5.0                                            base         q.s           q.s                                                ______________________________________                                    

The three essential compounds in the composition of this invention are:

(I) 1,5-dihydroxynaphthalene, (II) m-aminophenol and (III)p-aminodiphenylamine or a suitable acid addition salt thereof asrepresented by the following formulas: ##STR1## wherein (HX) representsan optional suitable acid. Suitable acid addition salts include thosesalts formed by reacting any appropriate inorganic or organic acid whichforms a salt which is substantially non-toxic, non-irritating and stilleffective at the level employed. Particularly useful are the inorganicacid addition salts such as the hydrochloride, sulfates, hydrobromides,and the like. Preferred are the sulfates. Each compound may be readilyprepared by means known in the art or are available through chemicaloutlets such as Aldrich Chemical C., Inc. The dye base which is used inthe composition of this invention can be any suitable, compatible basewhich is generally known in the art, and will contain several componentswhich may include a fatty acid in the form of soap, syntheticdetergents, a gelling or thickening agent, a solvent, a leveling agent,a hair conditioning agent and other additives such as antioxidants,oxidation, retarders, chelating agents, pH adjusters and a perfume. Inmany cases the component which would fall into one category also fallsinto another category. Thus a fatty acid used in a base which usesammonia as the pH adjuster may appear as ammonium oleate and thus act asa surfactant. Representative bases may be prepared employing theprinciples set forth in The Chemistry and Manufacture of Cosmetics,ibid.

Suitable fatty acids include oleic acids, palmitic acid, stearic acid,lauric acid and coconut fatty acids. NoOrmally these are used as theammonium salt. These generally are good solvents and aid in dispersionof the dye intermediates and other ingredients in the product.

The surfactants used in the base may be on-ionic, anionic, amphoteric orcombinations thereof. The surfactants serve as penetrants, dyedispersing agents, coupling agents, foam and cleansing agents (inshampoo-- in colors) and they are often an essential part of thegelation system. Surfactants may include higher alcohol sulfates,ethoxylated nonylphenols, ethoxylated fatty eters, amphoterics, and thelike. Particularly valuable is polyethylene glycol p-nonylphenol etherhaving four ethylene glycol units (IGEPAL.sup. ® CO-430), polyethyleneglycol (3) lauryl amide (Amidox L₂) and ammonium lauryl sulfate(Carsonal ALS.)

Gelling agents can be employed if a gel is desired for the base. In thiscase a fatty alcohol such as oleyl alcohol can be employed. Ethoxylatedfatty alcohol may also be used along with alkylol amides. Gelling agentsserve as thickeners, solubilizers an foam stabilizers. Oleyl alcohol hasbeen found to be particularly valuable.

Solvents are employed in the base both to solubilize the dyeintermediates as well as the water immisible components in the dye base.The referred solvents are the lower alcohols, glycols, and glycolethers. For example, ethanol, propylene glycol, isopropyl alcohol andglycerine. Glycerine also acts as a humectant. Isopropanol, propyleneglycol, an glycerine are preferred.

Leveling agents as such are seldom included in the dye base compositionbecause many of the other ingredients perform this function, for exampleany of the solvents are useful as leveling agents. Fatty alcohols, fattyesters, alkylol amides and glycols all act to slow down the fusion ofthe intermediates into the hair and level absorbtion of the colors.

Many of the ingredients already mentioned also serve as hairconditioning agents. Other ingredients that can be used specifically forthis purpose not mentioned hereinbefore include lanolin derivatives,proteins and polyvinylpyrrolidone.

Antioxidants are often added to the base to prevent air oxidation andthe resulting deterioration of the product. Generally the most widelyused antioxidants are the alkali metal sulfites, BHA or BHT,specifically sodium sulfite. The amount of the antioxidant used issufficient to protect the product during the manufacture and to takecare of oxygen in the head space of the bottle. Generally this amount isless than 1% and usually is not more than 0.5%. Other antioxidantsinclude certain mercaptans (such as thioglycolic acid) ascorbic acid and2,3-dihydroxynaphthalene.

In addition to the antioxidant, other components may be added asoxidation retarders. If oxidation takes place too rapidly beforeadequate diffusion of the dye intermediates into the hair can takeplace, weaker and uneven dyeing may result. Thus, additives are includedwhich slow down the oxidation somewhat so that the color is developedonly after the dye is sufficiently diffused into the hair. Antioxidantswill act as retarders in certain instances, but specific retarders maybe included such as polyhydroxyphenols, 1-phenyl-3-methyl-5-pyrazoloneand the like.

Also included in the base may be chelating agents which are used to tieup trace quantities of heavy metals which can catalyze the decompositionof the perioxide once the peroxide is mixed with the dye. Generally themost useful chelating agents are the di-, tri- or tetra-sodium salt ofethylenediaminetetraacetic acid (EDTA).

The dye base and final dye composition is preferably quite alkalinehaving a pH of 9.0 to about 10.5. The high alkalinity is necessarybecause oxidation occurs more readily in an alkaline system and atalkaline pH's, the hair softens and swells making it more receptive tothe dye. The most commonly used alkali is ammonium hydroxide. Not onlyis it a good pH adjuster but it also is an effective swelling agent.Other additives such as alkylol amines can be used in addition to or inplace of ammonia.

Finally, if desired a perfume can be added. A suitable perfume should beunaffected by the alkaline product and should be relatively unaffectedby the peroxide during the short period of time that the dye bath isapplied to the hair. Perfume compounds should be free of aldehydes whichmay react with amino compounds and cause difficulty.

In preparing the base composition, the ingredients (save for the pHadjuster and the perfume) are placed together in a suitable mixingvessel, heated to the necessary temperature generally about 50° to 175°Farenheit and stirred for about 20 to 60 minutes, generally about 30minutes being sufficient. The base is then ready for the othercomponents of the composition to be added thereto.

In addition to the base composition as well as the three essentialingredients to obtain the brown dye, other ingredients also included inthe composition are modifiers and couplers. Modifiers and couplers areadded to produce desirable color modifications as well as to serve ascolor stabilizers, antioxidants and retarders. For the purposes of thisinvention modifiers are defined as secondary dye intermediates which arehydroxylated aryl groups and include such compounds as pyrocatechol(1,2-benzenediol), resorcinol (1,3-benzenediol), chlororesorcinol,hydroquinone (1,4-benzenediol), pyrogallol (1,2,3-benzenetriol),phloroglucinol (1,3,5-benzenetriol), 1-naphthol,1,3-dihydroxynaphthalene, 1,7-dihydroxynaphthalene,2,7-dihydroxynaphthalene and glycin (N-(p-hydroxyphenyl)glycine). Ofthese modifiers those particularly valuable in this instance areresorcinol, 2,7-dihydroxynaphthalene, 1,7-dihyroxynaphthalene,pyrocatechol, phluroglucinol and glycin. Generally the modifier will bepresent in an amount of about 1.0 to 15.0 pbw and preferably 1.2 toabout 11.0 pbw in the total composition. A particularly valuablecombination (in 100 parts of total composition) contains:

0.30- 2.50 pbw of 1,7-dihydroxynaphthalene,

0.20- 1.00 pbw of 2,7-dihydroxynaphthalene,

0.20- 2.00 pbw of resorcinol,

0.20- 2.00 pbw of pyrocatechol,

0.20- 2.00 pbw of phluroglucinol, and

0.10- 1.50 pbw of glycin.

Suitable couplers include primary dye intermediates such as o- andp-aminophenols and suitable acid addition salts thereof such as thehydrochlorides and sulfates and secondary dye intermediates such asm-aminophenols. Generally the coupler is present at about 0.5- 7.5 pbwand preferably 0.6- 5.0 pbw. Particularly valuable are m-aminophenol,p-methylaminophenol sulfate, o-aminophenol, and the like. A particularlypreferred modifier consists of

0.2-2.0 parts by weight of p-aminophenol,

0.2 to 2.0 parts by weight of p-methylaminophenol sulfate, and

0.2 to 1.5 o-aminophenol.

The composition of the invention is prepared by mixing the base asprepared as discussed hereinbefore with the essential ingredients andthe modifiers and couplers at a temperature of about 50° to 200°Farenheit, preferably about 150° F. for a time sufficient to form ahomogeneous mixture. This time will generally be less than two hours andusually will be ready in about one-half hour depending on the size ofthe batch which is being prepared.

The resulting composition is then mixed with a suitable oxidizing agentsuch as peroxide. Generally equal amounts of the dye composition aremixed with the peroxide as a 6% solution in water and the resultingmixture is then placed in contact with the hair which is to be dyed fora time sufficient to effect dyeing thereof. This will generally be about20 to 60 minutes depending upon the depth which is desired. Generallythe time will be about 30 minutes to 45 minutes. Thereafter the dyecomposition is washed off the hair so dyed.

Thus, a composition has been described which is essentially free ofmutagenic phenylenediamines, derivatives thereof and nitro compounds.The composition is found to have little or no irritancy or sensitizationand does not result in damage to the hair. It is easy to apply in ashort period of time, has good stability and produces the illusion ofnatural color on the hair. It has a high degree of coverage, does notstain the scalp and is permanent under normal conditions. It is found tobe fast to light, perspiration and shampooing.

Preparation of a Suitable Base

The following substances are measured and placed in a suitable mixingvessel

    ______________________________________                                                           Parts of Weight                                            ______________________________________                                        Amidox L.sub.2       7.00                                                     Propylene Glycol     12.00                                                    Oleyl Alcohol        10.00                                                    Glycerine            6.00                                                     Igepal CO-430        4.00                                                     Carsonol ALS Spec.   20.00                                                    Isopropyl Alcohol    14.00                                                    Perfume              0.30                                                     Sodium Sulfite       0.20                                                     Trisodium EDTA       0.10                                                     Water, Deionized     20.40                                                    Ammonia 28%          6.00                                                     TOTAL                100.00                                                   ______________________________________                                    

The mixture is heated to 150° for 30 minutes while stirring regularlyuntil a homogeneous mixture is obtained. This mixture is then used toprepare the composition of the invention.

The following example is given as a representation of the composition ofthe invention but is not to be read in a limiting sense.

EXAMPLE 1 Preparation of a Composition of the Invention

The following amounts of ingredients are preweighed in a suitable vesseland added to sufficient quantity of the base prepared according to theabove Preparation to make a total of a 100 gram mixture of a compositionuseful for a very dark brown hair dye.

    ______________________________________                                        1,5-dihydroxynaphthalene                                                                              2.00 gm                                               p-aminodiphenylamine sulfate                                                                          0.40 gm                                               m-aminophenol           0.60 gm                                               p-methylaminophenol sulfate                                                                           0.26 gm                                               1,7-dihydroxynaphthalene                                                                              1.80 gm                                               2,7-dihydroxynaphthalene                                                                              0.24 gm                                               o-aminophenol           0.40 gm                                               resorcinol              0.30 gm                                               ______________________________________                                    

EXAMPLE 2 Preparation of a Composition of the Invention

The following amounts of ingredients are preweighed in a suitable vesseland added to sufficient quantity of the base prepared according to theabove Preparation to make a total of a 100 gram mixture of a compositionuseful for a dark brown hair dye.

    ______________________________________                                        1,5-dihydroxynaphthalene                                                                              0.33 gm                                               p-aminodiphenylamine sulfate                                                                          0.40 gm                                               m-aminophenol           0.40 gm                                               p-methylaminophenol sulfate                                                                           0.13 gm                                               1,7-dihydroxynaphthalene                                                                              0.47 gm                                               resorcinol              0.40 gm                                               p-aminophenol           0.40 gm                                               pyrocatechol            0.26 gm                                               ______________________________________                                    

EXAMPLE 3 Preparation of a Composition of the Invention

The following amounts of ingredients are preweighed in a suitable vesseland added to sufficient quantity of the base prepared according to theabove Preparation to make a total of a 100 gram mixture of a compositionuseful for a dark warm brown hair dye.

    ______________________________________                                        1,5-dihydroxynaphthalene                                                                              0.80 gm                                               p-aminodiphenylamine sulfate                                                                          0.40 gm                                               m-aminophenol           0.80 gm                                               p-methylaminophenol sulfate                                                                           0.36 gm                                               1,7-dihydroxynaphthalene                                                                              0.80 gm                                               2,7-dihydroxynaphthalene                                                                              0.50 gm                                               p-aminophenol           0.80 gm                                               pyrocatechol            0.40 gm                                               ______________________________________                                    

EXAMPLE 4 Preparation of a Composition of the Invention

The following amounts of ingredients are preweighed in a suitable vesseland added to sufficient quantity of the base prepared according to theabove Preparation to make a total of a 100 gram mixture of a compositionuseful for a medium brown hair dye.

    ______________________________________                                        1,5-dihydroxynaphthalene                                                                              0.60 gm                                               p-aminodiphenylamine sulfate                                                                          0.25 gm                                               m-aminophenol           0.50 gm                                               p-methylaminophenol sulfate                                                                           0.20 gm                                               o-aminophenol           0.40 gm                                               p-aminophenol           0.60 gm                                               resorcinol              0.20 gm                                               ______________________________________                                    

EXAMPLE 5 Preparation of a Composition of the Invention

The following amounts of ingredients are preweighed in a suitable vesseland added to sufficient quantity of the base prepared according to theAbove Preparation to make a total of a 100 gram mixture of a compositionuseful for a light golden brown hair dye.

    ______________________________________                                        1,5-dihydroxynaphthalene                                                                              0.30 gm                                               p-aminodiphenylamine sulfate                                                                          0.06 gm                                               m-aminophenol           0.56 gm                                               p-methylaminophenol sulfate                                                                           0.18 gm                                               o-aminophinol           0.06 gm                                               p-aminophenol           0.80 gm                                               phluroglucinol          0.27 gm                                               glycin                  0.08 gm                                               pyrocatechol            0.38 gm                                               ______________________________________                                    

EXAMPLE 6

Equal quantities of the composition of each of Examples 1-5 are mixedwith 6% aqueous hydrogen peroxide. The resulting mixture is applied toswatches of human hair for 30 minutes to give the followng results:

Example 1-- Darkest Brown

Example 2-- Dark Brown

Example 3-- Warm Brown

Example 4-- Medium Brown

Example 5-- Light Golden Brown.

The subject matter claimed is:
 1. A composition which, when combined with an oxidizing agent, dyes keratinous fibers brown, which composition is essentially free of o-, m- or p-phenylenediamine,2,4-diaminoanisole and nitro compounds, said composition consisting essentially of:about 0.1 to 4.0 parts by weight of 1,5-dihydroxynaphthalene; about 0.01 to 1.5 parts by weight of p-aminodiphenylamine or a suitable acid addition salt thereof; about 0.2 to 2.5 parts by weight of m-aminophenol; about 1.0 to 15.0 parts by weight of a suitable modifier; about 0.5 to 7.5 parts by weight of a suitable coupler; a sufficient amount of a suitable dye base to make up a total of 100 parts by weight of said composition.
 2. The composition of claim 1 wherein:0.25 to 2.5 parts by weight of 1,5-dihydroxynaphthalene, 0.05 to 1.0 parts by weight of p-aminodiphenylamine or a suitable acid addition salt thereof; and 0.2 to 2.0 parts by weight of m-aminophenol are employed.
 3. The composition of claim 1 or 2 wherein said modifier consists essentially of:0.30-2.50 parts by weight of 1,7-dihydroxynaphthalene, 0.20-1.00 parts by weight of 2,7-dihdyroxynaphthalene,
 0. 20-2.00 parts by weight of resorcinol,0.20-2.00 parts by weight of pyrocatechol, 0.20-2.00 parts by weight of phluroglucinol, 0.10-1.50 parts by weight of glycin.
 4. The composition of claim 1 or 2 wherein said coupler consists essentially of:about 0.2 to 1.5 parts by weight of o-aminophenol and about 0.2 to 2.0 parts by weight of p-aminophenol and about 0.2 to 2.0 parts by weight of p-methylaminophenol sulfate.
 5. The composition of claim 1 wherein said dye base consists essentially of:7.00 parts by weight of polyethylene glycol (3) lauryl amide, 12.00 parts by weight of propylene glycol, 10.00 parts by weight of oleyl alcohol, 6.00 parts by weight of glycerine, 4.00 parts by weight of polyethylene glycol p-nonylphenol ether having four ethylene glycol units, 20.00 parts by weight of ammonium lauryl sulfate 14.00 parts by weight of isopropyl acohol, 0.30 parts by weight of perfume, 0.20 parts by weight of sodium sulfite, 0.10 parts by weight of trisodium EDTA 20.40 parts by weight of deionized water, and, 6.00 parts by weight 28% aqueous ammonia.
 6. The composition of claim 5 for dyeing hair a very dark brown, said composition consisting essentially of:2.00 parts by weight of 1,5-dihydroxynaphthalene, 0.40 parts by weight of p-aminodiphenylamine sulfate, 0.60 parts by weight of m-aminophenol, 0.26 parts of weight of p-methylaminophenol sulfate, 1.80 parts of weight of 1,7-dihydroxynaphthalene 0.24 parts of weight of 2,7-dihydroxynaphthalene 0.40 parts of weight of o-aminophenol 0.30 parts of weight of resorcinol 94.8 parts of weight of the base of claim
 5. 7. The composition of claim 5 for dyeing hair a dark brown, said composition consisting essentially of:0.33 parts by weight of 1,5-dihydroxynaphthalene, 0.40 parts by weight of p-aminodiphenylamine sulfate, 0.40 parts by weight of m-aminophenol, 0.13 parts by weight of p-methylaminophenol sulfate, 0.47 parts by weight of 1,7-dihydroxynaphthalene, 0.40 parts by weight of resorcinol, 0.40 parts by weight of p-aminophenol, 0.26 parts by weight of pyrocatechol, and 97.21 parts of weight of the base of claim
 5. 8. The composition of claim 5 for dyeing hair a dark warm brown, said composition consisting essentially of:0.80 parts by weight of 1,5-dihydroxynaphthalene, 0.40 parts by weight of p-aminodiphenylamine sulfate, 0.80 parts by weight of m-aminophenol, 0.30 parts by weight of p-methylaminophenol sulfate,
 0. 80 parts by weight of 1,7-dihydroxynaphthalene,0.50 parts of weight of 2,7-dihdyroxynaphthalene, 0.80 parts by weight of p-aminophenol, 0.40 parts by weight of pyrocatechol, and 95.2 parts by weight of base of claim
 5. 9. The composition of claim 5 for dyeing hair a medium brown, said composition consisting essentially of:0.60 parts by weight of 1,5-dihydroxynaphthalene, 0.25 parts by weight of p-aminodiphenylamine sulfate, 0.50 parts by weight of m-aminophenol, 0.20 parts by weight of p-methylaminophenol sulfate, 0.40 parts by weight of 1,7-dihydroxynaphthalene, 0.60 parts of weight of 2,7-dihydroxynaphthalene, 0.20 parts of weight of 0-aminophenol and 97.25 parts of weight of the bae of claim
 5. 10. The composition of claim 5 for dyeing hair a light golden brown, said composition consisting essentially of:0.30 parts by weight of 1,5-dihydroxynaphthalene, 0.06 parts by weight of p-aminodiphenylamine sulfate, 0.56 parts by weight of m-aminophenol, 0.18 parts by weight of p-methylaminophenol sulfate, 0.06 parts by weight of 1,7-dihydroxynaphthalene, 0.80 parts of weight of 2,7-dihydroxynaphthalene, 0.27 parts by weight of resorcinol, 0.08 parts by weight of p-aminophenol, 0.38 parts by weight of pyrocatechol, and 97.31 parts by weight of the base of claim
 5. 11. A process for dyeing keratinous fibers brown, which process comprises contacting said fiber with an effective amount of a composition of claim 1 and an oxidizing amount of a suitable oxidizing agent for a time sufficient to effect dyeing.
 12. The process of claim 11 wherin said keratinous fiber is human hair.
 13. A hair dye composition consisting essentially of the composition of claim 1 and a suitable oxidizing agent. 